Succinimide-containing dyestuffs

ABSTRACT

Dyestuffs of the formula:   WHEREIN R represents a hydrogen atom or an alkyl or alkyl-Oalkyl group, the alkyl groups containing one to four atoms of carbon, R1 represents a hydrogen atom or a methyl group, R2 represents a alkyl group containing one to four carbon atoms, or a cycloalkyl, aryl, aralkyl or succinimidoethyl group, Y represents a hydrogen or halogen atom or an alkoxy, nitro, cyano, or amino group, and X represents a monovalent anion and processes for their manufacture. These dyestuffs are particularly suitable for the coloration of fibers based on polymers or copolymers of acrylonitrile.

United States Patent 1 1 Kremer 1 Jan. 30, 1973 1 SUCCINIMlDE-CONTAINING DYESTUFFS [75] Inventor: Gilbert Victor Henri Kremer, 95 Ermont, France [73] Assignee: Ugine Kuhlmann, Paris, France 22 Filed: on. 1, 1969 [21] Appl. No.: 862,921

[30] Foreign Application Priority Data [58] Field of Search.....260/326.5 FM, 326.3, 310 R, 260/2472 A, 293.7]

[56] References Cited UNITED STATES PATENTS 3,299,096 1/1967 Zienty et al. ..260/326.3

Primary Examiner-Alex Mazel Assistant ExaminerJoseph A. Narcavage Att0rneyBeveridge & Degrandi [57] ABSTRACT Dyestuffs of the formula:

w, "NR3: I; e

:N R, R Y 0 Y \Qp/ 1 J cH2 Rx CzH4-N\ J:

C[ H2 6 X wherein R represents a hydrogen atom or an alkyl or alkyl-O-alkyl group, the alkyl groups containing one to four atoms of carbon, R represents a hydrogen atom or a methyl group, R represents a alkyl group containing one to four carbon atoms, or a cycloalkyl, aryl, aralky] or succinimidoethyl group, Y represents a hydrogen or halogen atom or an alkoxy, nitro, cyano, or amino group, and X represents a monovalent anion and processes for their manufacture.

These dyestuffs are particularly suitable for Y the coloration of fibers based on polymers or copolymers of acrylonitrile.

9 Claims, No Drawings SUCClNlMIDE-CONTAINING DYESTUFFS The present invention relates to dyestuffs, their preparation and use.

According to the present invention dyestuffs are provided of the general formula:

/R 3 z Y x- R C2H4N\ l I Xe in which R represents a hydrogen atom or an alkyl or alkyl-O-alkyl group, the alkyl groups containing one to four carbon atoms, R, represents a hydrogen atom or a methyl group, R represents an alkyl group containing one to four carbon atoms, or a cycloalkyl, aryl, aralkyl or succinimido-ethyl group, Y represents a hydrogen or halogen atom or an alkoxy (containing one to four carbon atoms), nitro, cyano, or amino group and X represents a monovalent anion.

Examples of cycloalkyl, aralkyl or aryl groups represented by R are the cyclohexyl, benzyl and phenyl groups and phenyl groups substituted by non-watersolubilizing substituents, such as halogen atoms and alkyl and alkoxy groups containing one to four carbon atoms.

The amino group entering into the definition of Y may be a simple amino group or an amino group of the formula:

wherein R is a hydrogen atom or an alkyl or an alkyl group, R represents an alkyl, cycloalkyl (such as for example cyclohexyl) or aryl group or a heterocyclic residue, or R and R,, with the nitrogen atom form a heterocyclic radical, such as for example morpholino or piperidono. The aryl groups may be for example phenyl, diphenyl or naphthyl groups which may be substituted by at least one non-ionic substituent such as for example a halogen atom or an alkyl, alkoxy, acyl, acylamino, dialkylamino or alkyl (aryl) amino group, the alkyl and alkoxy groups having one to four carbon atoms.

The anion does not possess any tinctorial property; it is preferably selected from anions giving water-soluble salts of dyestuffs. For example, the chloride, bromide,

sulphate, phosphate, acetate, formate, oxalate and chlorozincate anions may be mentioned.

The dyestuffs of formula (I) dye fibers based on polymers or copolymers of acrylonitrile in blue and green shades with good fastness and good stability toartificial light. Among these dyestuffs, those of the following formula are particularly advantageous on account of their affinity for the said fibers:

in which formula R, represents a hydrogen atom or a methyl group, R represents a hydrogen atom or an alkyl group containing one to four carbon atoms, R"- represents an alkyl residue containing one to four carbon atoms, R, represents an alkyl group containing one to four carbon atoms, a cycloalkyl (for example cyclohexyl) or aralkyl (for example benzyl) group, or an aryl group, preferably a phenyl group, which may be substituted by non-water solubilizing substituents such as halogen atoms or the alkyl and alkoxy groups containing one to four carbon atoms, Y represents a hydrogen or halogen atom or an alkoxy(containing one to four carbon atoms), nitro, cyano or arylamino group, and X represents a monovalent anion.

The dyestuffs of formula I possessing two 2,5'-dioxopyrrolidinylethyl groups can be prepared, for example, by condensing'a N-(B-succinimidoethyl)aniline of the general formula:

O -CHQ C Hz (III) in which R and R, have the same significance as above, with a benzaldehyde, and oxidation of the leuco derivative thus obtained. v

The dyestuffs of formula ll may be obtained for example by condensing an aminobenzophenone of the general formula:

or the formula:

with a primary or secondary amine.

French Pat. No. 954,752 has mentioned the possibility of dyeing textile articles based on copolymers of vinyl chloride and acrylonitrile by dyestuffs of the triphenylmethane series. The colorations obtained with the known dyestuffs of this type, however, are lacking in fastness to light.

Theinvention is illustrated by, but not limited to, the following Examples in which the parts given are parts by weight unless the contrary is indicated.

EXAMPLE 1 2H4-(succinimido) temperature. Then a solution of 30 parts of crystalline sodium sulphate in 200 parts of water is added. After stirring for 15 minutes, the insoluble lead sulphate is filtered off and washed on the filter with 1,300 parts of I water. The dyestuff is precipitated in the filtrate in the form of the chlorozincate by the successive addition of 300 parts of sodium chloride, then 20 parts by volume of a percent solution of zinc chloride. The product is stirred for an hour, then the dyestuff is isolated by filtration and washed on the filter with 500 parts of a 20 30 percent solution of sodium chloride. 87 parts by weight of the dyestuffldried in a hot-air oven, are obtained. It dyes fibers based on polymers or copolymers of acrylonitrile in bright yellow-green shades which are very fast to light.

EXAMPLE 2 On replacing the benzaldehyde in Example 1 by an equivalent amount of 3-nitrobenzaldehyde, a yellow green dyestuff of similar properties is obtained.

EXKMPLE 3 On replacing the benzaldehyde in Example 1 by an equivalent amount of 4-chlorobenzaldehyde, a dyestuff washed on the filter with water and dried in a hot-air 45 of the following formula is obtained:

. CH3 7 V /C2H5 3 =N\ /CCH2 2 Hl I c-om t l, ZnCla C2115 f (I: C2H4-N l CCH2 0 1t dyes fibers based on polymers or copolymersof acrylonitrilea yellow-green shade which is very fast to light. 1

EXAMPLE 4 40 parts of the dyestuff of Example 3 are dissolved in 25 parts of water acidified with one part of concentrated hydrochloric acid: 14 parts of p-toluidine are added to this solution, then it is heated at C. until the presence of the initial green dyestuff is no longer detected by paper chromatography. The mixture is then run into 3,000 parts of hot water acidified with 30 parts of acetic acid, and the solution is clarified by filtering while hot. To the cooled filtrate are added l parts of sodium chloride, and the precipitated dyestuff is isolated by filtration, washed on the filter with a percent solution of sodium chloride and dried at 60C. in a hot-air oven. It dyes fibers based on polymer or copolymers of acrylonitrile in very bright blue shades which are stable to artificial light and fast to light.

The following Table tabulates further Examples of analogous dyestuffs prepared as in Example 4, but by replacing the p-toluidine by the amines YH indicated in toluidine and the 10.6 parts of benzaldehyde by 14.1 parts of p-chlorobenzaldehyde, and following the method of operation described in Example 1 a dyestuff of the following formula is obtained.

It dyes fibers based on polymers or copolymers of acrylonitrile a yellow-green shade which is very fast to light.

EXAMPLE 17 On reacting 41 parts of the dyestuff of Example 16 with 14 parts of p-toluidine under the conditions described in Example 4, a dyestuff is obtained which dyes fibers based on polymers or copolymers of acrylonitrile a bright blue shade, which is fast to light.

EXAMPLE 18 On replacing the p-toluidine in Example 17 by an equivalent amount of p-anisidine, a dyestuff of the same tinctorial properties is obtained.

EXAMPLE 19 parts of 4-dimethylamino-benzophenone are mixed with 52 parts of N-ethyl-N-(2-succinimidoethyl)-m-toluidine and parts of phosphorus oxychloride, then the whole is heated at l00C. for several hours. 1000 parts of hot water are added to the still hot mixture, the solution obtained is allowed to cool and 100 parts of sodium chloride and 150 parts by volume of a 50 percent solution of zinc chloride are added. The dyestuff separates in a gummy form, and is isolated and redissolved in 2,000 parts of boiling water acidified with 50 parts of glacial acetic acid. The liquid obtained is clarified by filtering hot. The dyestuff is precipitated from the filtrate by the addition of 50 parts by volume of a 50 percent solution of zinc chloride, then isolated by filtration, and is finally washed on the filter with a 20 percent solution of sodium chloride and dried. It has the following formula:

Inc-p lt dyes fibers based on polymers or copolymers of acrylonitrile a yellow-green shade having good general fastness, especially to light.

The following Table summarizes some Examples analogous to the Example 19, the dyestuffs being prepared by using other benzophenones.

ZnCla Exam- Benzophenone Shade of the dyestuff plc on acrylic fibers 55 20 4-diethylamino-benzophenone yellow green 2l 4-diethylamino-2-methylbenzophenone yellow green 22 4-dimethylamino-4-chlorobenzo henone bright green 23 4-die ylamino-2-methyl-4'- chloro-benzophenone bright yellow green EXAMPLE 2 1 A mixture of 22 parts of the dyestuff of Example 22, 15 parts of p-anisidine, 60 parts of water and 0.5 parts of concentrated hydrochloric acid is heated for 5 hours at C.

The reaction mixture is then poured into 1,000 parts of hot water acidified with 50 parts of acetic acid, and 100 parts of sodium chloride are added. The dyestuff is precipitated and is isolated by filtering in the cold, and is washed on the filter with a 3 percent solution of sodium chloride and dried at 60C. It dyes acrylic fibers a bright blue shade which is fast to light.

Examples similar to Example 24 are grouped in the following Table, the dyestuffs being prepared by replacing the p-anisidine by another aromatic amine.

Ex- Amine used Shade of the dyestuff on ample acrylic fibers 25 paratoluidine bright blue 26 aniline blue I claim:

1. A dyestuff of the formula:

I H2 l) X wherein R represents hydrogen or an alkyl or alkyl-O- alkyl group, the alkyl groups containing one to four carbon atoms, R, represents hydrogen or methyl, R represents an alkyl group containing one to four carbon atoms, cyclohexyl, benzyl, succinimidoethyl, phenyl, or phenyl mono-substituted by halogen or alkyl or alkoxy containing one to four carbon atoms, Y represents hydrogen, chlorine, alkoxy containing one to four carbon atoms, nitro, cyano, NH 3,5-dimethyl-4- pyrazolylamino, piperidino, morpholino, or the group NR R, wherein R represents hydrogen or alkyl containing one to four carbon atoms and R, is alkyl containing one to four carbon atoms, cyclohexyl, phenyl, diphenyl, naphthyl, or phenyl, mono-substituted by halogen, alkyl containing one to four carbon atoms, alkoxy containing one to four carbon atoms or acetylamino, and X represents a water-soluble noncoloring monovalent anion.

2. A dyestuff according to claim 1 corresponding to the formula:

R1 7 e v /R v =N C i: Y' o /RII (I? 7 @rk -4111; R C2H4N l l V H2 wherein R, represents a hydrogen atom or a methyl group R represents a hydrogen atom or an alkyl group containing one to four carbon atoms, R" represents an alkyl residue containing one to four carbon atoms, R, represents an alkyl group containing one to four carbon atoms, cyclohexyl, benzyl, phenyl or phenyl mono-sub stituted by halogen or alkyl or alk'oxy containing one to four carbon atoms, Y represents hydrogen, halogen, alkoxy containing one to four carbon atoms, nitro, cyamo, phenylamino, or phenylamino mono-substituted by halogen or alkyl or alkoxy containing one to four carbon atoms and X represents a water-soluble non-coloring monovalent anion.

3. A dyestufi on the formula:

in which R represents hydrogen, alkyl containing one to four carbon atoms, or alkyl containing one to four carbon atoms substituted by alkoxy containing one to four carbon atoms, Y represents hydrogen, chlorine, nitro, alkoxy containing one-to four carbon atoms, amino, 3,5-dimethyl-4-pyrazolylamino, piperidino, morpholino, or the group NR,',R wherein R represents hydrogen or alkyl containing one to four carbon atoms and R represents alkyl containing one to four carbon atoms, cyclohexyl, phenyl, diphenyl, naphthyl, or phenyl, mono-substituted by halogen, alkyl containing one to four carbon atoms, alkoxy containing one to four carbon atoms or acetylamino, and X represents a water-soluble non-coloring monovalent anion.

4. A dyestuff of the formula:

in which R is hydrogen or alkyl containing one to four wherein XOis the chlorozincate anion.

7. The dyestuff of the formula:

ing monovalent anion.

5. The dyestuff of the formula:

in which X9 is the chlorozincate anion.

8.-The dyestuff of the formula:

in which X is the chlorozincate anion.

6. The dyestuff of the formula:

in which X0 is the chloride anion. 

1. A dyestuff of the formula:
 2. A dyestuff according to claim 1 corresponding to the formula:
 3. A dyestuff on the formula:
 4. A dyestuff of the formula:
 5. The dyestuff of the formula:
 6. The dyestuff of the formula:
 7. The dyestuff of the formula:
 8. The dyestuff of the formula: 